Method and apparatus for thermal swing adsorption and...

Gas separation: processes – Solid sorption – Including reduction of pressure

Reexamination Certificate

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C095S106000, C095S115000, C095S116000, C429S006000, C429S006000

Reexamination Certificate

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06746515

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to adsorption apparatus and methods of gas adsorption.
BACKGROUND OF THE INVENTION
Separations of gases have long been important in many industrial processes. Removal of carbon dioxide continues to be an important objective for purifying air for humans to live underwater and in space. Other important technologies that can utilize improvements for gas separation include: fuel cells, ammonia production, fertilizer manufacture, oil refining, synthetic fuels production, natural gas sweetening, oil recovery and steel welding.
The adsorption capacity of a gaseous species onto an adsorbent is commonly expressed in graphical form in adsorption isotherms and isobars, which are widely published in the literature and by adsorbent manufacturers and suppliers. For the sorption of gas species, the capacity is typically expressed as the equilibrium mass of the species sorbed per unit mass of adsorbent (e.g., kg species/100-kg adsorbent). The sorbent capacity varies as a function of temperature and the partial pressure (concentration) of the species being sorbed. Loading or capacity typically increases as the adsorbent bed temperature decreases or the partial pressure of the sorbed species in the gas phase increases.
The variation of adsorption capacity with temperature and pressure can be used to effect separations of gas species. For example, in pressure swing adsorption (PSA) gas species are adsorbed onto a sorbent at relatively high pressure, tending to remove the species from the feed stream. In a regenerative PSA process, reducing the absolute pressure (e.g., applying a vacuum) to the loaded sorbent bed or reducing the partial pressure of the sorbed species in the gas phase by sweeping a lower concentration purge gas through the bed regenerates the sorbent. Cycle times for PSA processes are typically measured in minutes (Humphrey and Keller, “Separation Process Technology, McGraw-Hill, 1997). In a regenerative temperature swing or thermal swing (TSA) adsorption process, species are adsorbed at low temperature where the loading capacity is relatively high and (at least partially) desorbed at higher temperature, thus recovering sorption capacity for additional cycles.
In addition to gas species separations, TSA can be used to thermochemically compress gases. Sorption based thermochemical compression is applicable to refrigeration and heat pump cycles (e.g., see Sywulka, U.S. Pat. No. 5,419,156) and for chemical processing in general.
Gas adsorption is known to be applicable to a wide range of gas species (see, e.g., Kohl and Nielsen, Gas Purification, 5th Ed., Gulf Publ. Co., Houston, Tex.). Kohl and Nielsen report that in conventional TSA gas purification processes, adsorbent bed loading and unloading cycles are typically on the order of hours.
Despite their long-known use and importance, multiple problems remain with gas adsorption separation technologies. These problems include: use of excess energy, bulky apparatus or low capacity, cost, and slow rate and/or low mass of gas separated.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides a sorption pump that includes an adsorption layer comprising an adsorption mesochannel containing adsorption media, and a heat exchanger in thermal contact with the adsorption layer. The heat exchanger includes at least one microchannel. The adsorption layer has a gas inlet such that gas directly contacts the adsorption media without first passing through a contactor material.
In another aspect, the invention provides gas adsorption and desorption apparatus that includes at least one adsorption layer comprising an adsorption mesochannel containing adsorption media. The adsorption mesochannel has dimensions of length, width and height; wherein the height is at least 1.2 mm. The apparatus possesses capability such that, if the adsorption media is replaced with an equal volume of 13×zeolite, having a bulk density of about 0.67 grams per cubic centimeter, and then saturated with carbon dioxide at 760 mm Hg and 5° C. and then heated to no more than 90° C., at 760 mm Hg, then at least 0.015 g CO
2
per mL of apparatus is desorbed within 1 minute of the onset of heating. By heated to “no more than 90° C.” typically means that 90° C. water is passed through the heat exchanger; however, the phrase also encompasses heating by other means such as an electrically-resistive heater. Preferably, the apparatus includes at least one heat exchanger in thermal contact with the adsorption layer. In preferred embodiments, the apparatus possesses capability such that, if the adsorption media is replaced with an equal volume of 13x zeolite, having a bulk density of about 0.67 grams per cubic centimeter, and then exposed to carbon dioxide at 760 mm Hg and 5° C. for 1 minute and then heated to no more than 90° C., at 760 mm Hg, then at least 0.015 g CO
2
per mL of apparatus is desorbed within 1 minute of the onset of heating.
In yet another aspect, the apparatus is configured to selectively heat the adsorbent. By “selectively” it is meant that the apparatus is configured to heat the adsorbent material in preference to other parts of the apparatus; more particularly, where the adsorbent occupies only a portion of the adsorbent layer, heat is added to the adsorbent in preference to other parts of the adsorbent layer. For example, the at least one heat exchanger could be configured such that the heat exchange fluid flow paths substantially overlap the area of adsorption channel or channels. Alternatively, the apparatus could contain a relatively thermally conductive material overlapping the adsorption channel or adsorption channels and a relatively thermally insulating material that does not substantially overlap the adsorbent channel or adsorbent material. By “substantially overlap” it is meant that, when viewed from a direction perpendicular to the direction of flow in which the adsorption channel and heat exchanger is stacked, the areas of the adsorbent channel(s) and the thermally conductive material have at least about an 80% overlap.
In a further aspect, the invention provides a sorption pump, that includes an adsorption layer comprising an adsorption channel containing adsorption media, and a mesochannel heat exchanger in thermal contact with the adsorption layer. The mesochannel heat exchanger has a fluid flowing therethrough that has a high thermal diffusivity, such that the characteristic heat transport time for the fluid in combination with the mesochannel heat exchanger is no greater than 10 seconds.
The invention also provides an apparatus in which adsorption/desorption cells are connected to improve overall energy efficiency. Each cell contains at least one adsorption mesochannel having an inlet and/or outlet. Typically, each cell contains multiple adsorption mesochannels that share a common header and common footer, and that are operated together. Preferably, each adsorption channel is in thermal contact with at least one heat exchanger. Each adsorption channel contains adsorption media. Typically, the apparatus also contains or is used in conjunction with a heat source and a heat sink. In some embodiments, the heat sink could be the non-adsorbed gas, which is passed through and removed from the apparatus. The apparatus contains heat transfer conduits between each cell and the heat source and heat sink and also contains heat transfer conduits between each cell and at least two other cells. In operation, the conduits carry a heat exchange fluid or can contain a thermally conductive material. The apparatus also contains valves that can control gas flow into the at least one adsorption channel. Cell volume is defined as the volume of the adsorption channel or channels that are operated together, including the volume of the heat exchange channel or channels, the volume between such channels, the volume of the outer walls of the cells, and the volume of inlet and outlet footers, when present.
The invention further provides a method of gas adsorption and desorption, comprising passing a gas into an a

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